Method and apparatus for measuring ion-concentration



Feb. 15, 19,38. E. D. DoYLE ET AL METHOD AND APPARATUS FOR MESURING ION CONCENTRATION1 Filed Jan. 11, 1936 I SW1 Patented Feb. 15, 1938 t UNITED STATES l PATENT OFFICE v l 2,108,294 METHOD AND APPARATUS non MEASUMNG ION-coucEN'rnsTloN sylvania Application January 11,1936, Serial N0. 58,623

I somma. mi.. eos-s) g the sudewire ce is suitably calibrated, as herein- Our invention relates to methods of and apparatus for measuring the ion-concentration of a solution. f

In accordance with our invention, the solution may be continuously supplied by a suitable sysf tem. of pipes, conduits or the like, to an ion-concentration cell included in an electrical measuring system, and to avoid false measurements due to extraneous potentials, it is provided that at least one of the systems has high insulation resistance to ground. v

More particularly in accordance with our invention, to avoid potential effects unrelated to. the ion-concentration of the solution, the electrodes of melon-concentration cell are isolated from ground, and when the solution owsvthrough a grounded conduit, it is delivered to,

and discharged from the ion-concentration cell in streams which are broken .up into drops o which are equivalently discontinuous.l

20 More particularly, ethevelectrodes of the. ionconccntration cell lare connectedin' circuit with the input electrodes oi' an amplier tube, preferably of a type having high input impedance, and

,ance the voltage of said cell.

Our invention further resides in the features i trode and the solution whose ion-concentration is to be measured, is of insulating material, such as glass, bakelite,l or the like. The glass electrode y GE is connected. as by conductor i to the control ,electrode CE of a vacuum tube V, preferably oi the typeliaving a high input impedance, such as 45, the Westinghouse type DRH506 tube. The. input impedance of tube V is of the next order above the order ofthe impedance of the ion-concentration cell which is from about 2 to about 30 megohms. The other electrode of the cell I is'con- 50 nected by conductor 2 tothe contact P adjust' able along the slidcwire' CS connected through resistors RI, R4 to the cathode C of tube V. The slidewire' CS is connected in series with resistances R. Rl, R2, R3, RA across the source oi Ju voltage E. Current from the battery through a calibrated source of voltage, adjustable to balsive device, is connected to contact Pi adjustable along resistance R6, and to contact P2 adjustable along the slidewlre S in shunt to resistance -RL The output impedance of tube V is of an order substantially lower than the impedance oi the ion-concentration cell and therefore better suited to work into the network which includes the 'gelvanometer GA, or equivalent electroresponsive device.

To calibrate current through the slidewire CS,l

or the standard 'een sc, as indicated by anun r deection of galvanometer GA.

To adjust the system for the tube constants, the switch SW!! is closed to connect the control electrode CE to ground G. Then, for a desired setting of contact Pi, switch SW being in the upper position shown, the contact P2 is adjusted along slidewire S until there is a null deiiection oi" galvanometer GA.

As shown irl-Fig. l. the internal shieldIS ofthe tube is connected to ground. and calibrating source oi' potential CS, in the control electrode circuit of the tulris connected also to ground'G,

'as by conductor-t which extends to an interme.

diate point oi' resistance R5 which is in shunt'- to slidewire CS. l When the. ion-concentration cell is of thetype using av silver silver-chloride electrode, conductotl a 1s connected to a terminal of sudewire ce instead of to a point whose potential is intermediate the terminal potentials of the slidewire. i'ifterv the system has been calibrated and 'adjusted to thevtube constants, as described, theion-concentration of the solution in the cell-I is determined by adjusting contact P along slidewire CS until there is no galvanometer deiection. The ion-concentration, forA example, hydrogen ion-concentration, is then read in suitable umts from the scale or chart 9. The source of voltage E may, as shown,rbe a battery capable of supplying constant current for suitably long intervals of time. If desired, the battery may be connected across a charging system comprising rectiiers I0 supplied from a secondary of a transformer T connected to a suitable source of alternating voltage preferably through a `voltage regulating device VR. 'I'he amount of current supplied by the rectifier system may be adjusted by resistance Il. If desired, the batteryE may be allowed to float across .the charging system during measurements, particularly if voltage regulator VR or equivalent is used. With switch I2 open, the ammeter A indicates, the difference between charging or discharging of the battery. As shown, the cathode C of the tube may be heated from the same source of current E, and since the cathode of the particular tube shown is of the directly heated type, it is connected in series with resistances R-R5, intermediate the resistances R2, R3.` Y

Preferably, cond er K having a capacity of about 0.03 microf rad and an insulation `resistance of at least 200 megohms, is connected between the control electrode CE and the cathode C of the tube, and condenserKI having a capass alternating currents which may be induced/ in the leads to the electrodes CE and OE from neighboring circuits or electrical apparatus and which would otherwise be rectiied by the tube with consequent errors of measurement.

As thus far described, the ion-concentration v cell may be of type in which a batch of the solution whose ion-concentration is to be measured, is placed Within the housing of the ion-concentration cell. Since the housing, as above stated,W

is of insulating material, the electrodes in the solution therein are suitably insulated fromv ground; thus avoiding any faults of secondary potential effects Which would result in a false balance of the system and give an erroneous reading of the ion-concentration.

The system shown in Fig. 1, is adapted for 'measurement of the ion-concentration'of a solution iiowing in conduit GC grounded as conventionally shown by symbol Gl. Accordingly, the

vvhousing of the ion-concentration cell is provided with suitable inlets and outlets to allow a stream of the solution from the conduit to pass through the ion-concentration cell. The housing or,ow channel specically illustrated is of the type disclosed and claimed in co-pending application Serial No. 58,554, led January' 10, 1936. It is characteristic of the how-channel that the electrode GE is in a region of high turbulence' of the incoming solution and its sensitivity is therefore, maintained high to changes of lion-concentration. The turbulence is increased by the air entrained by the falling drops in tube I4.

A stream from the` solution flowing through grounded conduit GC is diverted therefrom by the pipe I2 preferably having a valve I3.v The end of pipe I2 terminates in the upper end of a chamber I4 suitably insulated Vfrom ground, the stream breaking into drops as it,falls into the lower end the chamber, the drops reforming into a stre m which ows through pipe I5 'to the inlet I6 of the flow-channel or housing F of theion-concentration cell.

'I-'he solution, upon entering the flow-channel,

and then. divides, part of the solution passing to the outlet pipe I'I from whose end it flows in a stream broken into drops vinto the collecting trough GT, or equivalent, which may be grounded as conventionally shown by symbol G2. The other portion of the stream passes through the intermediate pipe I8 into a second chamber FI of the' how-channel in which the reference electrode RE is disposed. The solution passes from chamber FI into the outlet pipe I9 from which it ilows in a stream, broken into drops, into the collecting trough GT or other collector which may be grounded as conventionally shown by symbol G2 and the solution in the flow-channel of the cell. Accordingly, there are avoided any secondary potential effects which would result in a false position of balanceof the contact P. For accurate measurements of the ion-concentration, it is essential that these false potential effects be avoided. Theoretically if either the system for supplying solution to the ion-concentration cell or the electrical system including the cell electrodes,.tube V and the network associated therewith, have high insulation resistance to'ground, or both have high insulation resistance to ground, these false eiects can beavoided. Practically, it is difcult or inconvenient to procure and main.. tain high 'insulation resistance of all components of lt-he measuring circuits and apparatus with respect to ground.\ In the preferred arrangement, the insulationresistance of .the system supplying solution to the cellis maintained high by breaking the supply and discharge stream into drops; the connection of the measuring cir- 'cuit to ground G is not essential, thoughv desirable.

When continuous measurementsl are to be made, there may be utilized 'recorder mechanism preferably of the type shown in Squibb Patent 1,935,732, having mechanical relay mechanism suited to effect adjustment of'contact P in, response to deflections of galvanometer GA. When a recorder of the Squibb type is used, the callbrating switch shown in Figs. 13 and 14'of the Squibb patent may be'used to adjust our systemfor any changes that may occur in the tube constants during operation. Specifically, the calibrating switch of the Squibb patent may be used I as our switch SW2 to effect intermittent energi- March 2, 1937,: of Albert J. Williams, Jr., owned by the assignee of the presenty application.

If desired, a control may be eiected in accordance with or in response to deflections of the galvanoineter; for example, automatic control of the ion-concentration may be eiected generally as shown in Keeler Patent No. 1,530,833.

The system shown in Fig. 2 is similar to that shown in Fig. 1 except the tube V is of the General Electric type FP54 having an accelerating grid SG which is connected to an intermediate tap of resistance R2. In this tube, the control electrode CE is a grid-element and the output electrode OE is a plate-element. The two grids and the plate are preferably by-passed by condensers K, KI and K2 having respectively capacities of the order of 0.003 microfarad, 1 microfarad and l microfarad. Condenser K should have highinsulation resistance, for example not less than about 200 megohms; a mica type condenser is usually satisfactory.

The calibration,'adjustment and operation of the system are substantially the same as described in connection with Fig. 1.

While preferred arrangements are illustrated, it is to be understood our invention is not limited thereto, ybut is coextensive in scope with the appended claims.

What we claim is:

1. A system for continuous measurement of the ion-concentration of a solution comprising an ion-concentration cell, a circuit including said ion-concentration cell and a calibrated source of variable voltage, means for indicating unbalance between the voltages of said source and said cell, means for insulating the electrodes of said cell from ground, and meanslfor feeding the solution to, and discharging it from, said cell in streams which are broken into drops to avoid a conductive path from said electrodes to ground through the solution.

2. A system for continuous measurement of the ion-concentration of a solution comprising an ion-concentration cell having a now-channel and electrodes disposed therein, a circuit including I said ion-concentration cell and a calibrated source of variable voltage and means for feeding the solution to,l and discharging it from, said dow-channel in streams which are broken into drops. l

3. A system for measurement of lthe ion-concentrationA of a. solution comprising an ion-concentration cell having a dow-channel and electrodes therein, a thermionic tube, connections from the electrodes of said cell to input electrodes oil-said tube, va calibrated source of voltage included in one of said connections and connected to ground, and means for feeding the solution to, and discharging it from, saidI now-channel in streams broken into drops.

4. A system for continuous measurement of the ion-concentration of a solution owing in a grounded conduit comprising an -ionconcentration cell having a now-channel and electrodes therein, athermionic tube, connections from the electrodes of said cell to input electrodes of said tube, a calibrated source of voltage included in an electrode of said cell, a calibrated source of voltage connected between the cathode of said tube and another electrode of said cell, a conncction'from an intermediate terminal of said source to ground, and means for delivering soluftion to said flow-'channel from said conduit and for discharging it from said now-channel in streams broken into drops. A

6. A system for continuous measurement of the ion-concentration of a solution flowing in a grounded conduit comprising an ion-concentration cell having a now-channel, a glass electrode, and a reference electrode,van electro-responsive device; a vacuum tube having an input impedance of the order of the impedance ofl said cell and an output impedance. of the order of the impedance of said electro-responsive device, connections for including saidelectro-responsive device in the output circuit of said tube, a connection from said glass electrode to the controlielectrode of said tube, a calibrated source of voltage connected to the cathode of said tube, a connection fromsaid reference electrode toan adjustable point of said source of voltage, a connection from saidsource of voltage to ground. and means for delivering solution from said conduit tovsaid ilowchannel and for discharging solution from said flow-channel lin streams which are broken into drops. r

7. A system for continuous measurement of the ion-concentration of a solution flowing in a grounded conduit comprising an ion-.concentra- 'tion' cell having a flow-channel and electrodes therein, a tube having a control electrode connected 4to an electrode of said cell,.a calibrated source of voltage connected between the cathode of Vsaid tube and another electrode of said cell, a connection -from a terminal of said source to ground, and means for delivering solution to said flow-channel from said conduit and for discharging it from said flow-channel in streams broken into drops. y

8 In the art of measuring the ion-concentra tion of a solution owing in' grounded conduit by a system including an ion-concentration'cell in the input system of a vacuum tube, the method of avoiding potential effects unrelated to the ionconcentration which comprises insulating the electrodes of said cell from ground, delivering 'the solution from said conduit to said cell in a stream i broken into drops, and dischargingthe solution from said cell in a. stream broken into drops.

D.'.DoYLE. GEORGEA PERLEY; 

